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261.
Self-diffusion coefficients of vanadium in the FeV -phase and in the corresponding -solid solution (Fe-47 wt.% V) measured in the temperature ranges 1002–1115 °C (-phase) and 1230–1320 °C are reported. The found results differ fundamentally and significantly from the relations in ordered and disordered solid solutions [9]. The diffusivity in -phase at the transition temperature (T
/=1200 °C) is cca 14 times lower than the diffusivity in the b.c.c. solid solution, the chemical composition of which is the same. The lowering is caused by the different values of frequency factors,D
O=0.11 cm2/s andD
O=45 cm2/s. The effect of the corresponding activation enthalpiesH
=252 kJ/mole andH
=293 kJ/mole is small and quite opposite. The occurence of higher activation enthalpyH
in the -solid solution at temperaturesT>T
/ may be attributed to a certain amount of the f.c.c. phase coexisting in the b.c.c. matrix at concentrationsc
v>27 wt.% at sufficiently high temperatures [7]. A comparison of vanadium self-diffusion characteristics measured in the -phase to the extrapolated values obtained on the basis of the previous measurements [1] in the Fe-V primary solid solutions 1 shows that the diffusivity ratioD
1/D
(1473 K)=33 and that the activation enthalpyH
is by about 3% higher than the valuesH
1 (eq. (5)) measured in the uniphase b.c.c. solid solutions. 相似文献
262.
A potassium electrode utilizing a solution of valinomycin in diphenylether and a porous membrane is compared with selectrodes in which the diphenylether has been replaced by a suitable plasticizer and the porous membrane support by a polymer net-work. The development of the polymer membrane allows the use of simplified selectrode construction with a “solid-state” calomel reference system; Rules for a successful choice of a suitable solvent-polymer combination are suggested and used for development of new Polyvinylchloride- and polyurethane-based membranes. 相似文献
263.
Ondřej Linhart Alžběta Kolorosová-Mrázová Jan Kratzer Jakub Hraníček Václav Červený 《Analytical letters》2019,52(4):613-632
An ultraviolet-photochemical generator (UV-PVG) capable of post-column on-line transformation of both organic and inorganic mercury species to cold vapor (Hg0) with subsequent detection by quartz tube-atomic absorption spectrometry (QT-AAS) was developed. Mercury(II), methylmercury(I), ethylmercury(I), and phenylmercury(I) were successfully detected after separation by reversed-phase high-performance liquid chromatography (RP-HPLC). Two types of AAS detectors were compared. The first was a commonly used line-source instrument while the second was a high-resolution continuum source (HR-CS) AAS. The latter provided better limits of detection: 0.47?µg?L?1 for Hg(II), 0.84?µg?L?1 for methylmercury(I), 0.80?µg?L?1 for ethylmercury(I), and 2.0?µg?L?1 for phenylmercury(I). The repeatability at 30?μg?L?1 was 3.6%, 4.1%, 6.2%, and 4.5% for these species (n?=?10). These figures of merit were comparable with those reported for more sensitive atomic fluorescence spectrometry. Nine sample extraction procedures were investigated. Extraction by tetramethylammonium hydroxide and HCl at 75?°C was selected as the only method compatible with the proposed separation and detection steps providing high extraction efficiency and no changes in mercury speciation. The applicability of the proposed high-performance liquid chromatography–ultraviolet-photochemical vapor generation–quartz tube-atomic absorption spectrometry method was demonstrated using fish samples and certified reference materials (CRM) DOLT-4 (dogfish liver) and ERM-CE464 (tuna fish). The results were comparable to those obtained by a reference method based on L-cysteine extraction and high-performance liquid chromatography–inductively coupled plasma-mass spectrometry (HPLC–ICP-MS) determination. 相似文献
264.
A pseudo-first-order catalytic mechanism in which both reactant and product of a redox reaction are strongly immobilized
on an electrode surface is theoretically analysed under conditions of square-wave (SWV) and staircase cyclic voltammetry (SCV).
A mathematical procedure is developed under diffusionless conditions. The relationships between the properties of the voltammetric
response and both the kinetic parameters of the redox reaction and the parameters of the excitation signal are studied. The
phenomenon of the quasi-reversible maximum is discussed. A comparative study between SWV and SCV is presented and the limitations
and advantages of both techniques, from analytical and kinetic points of view, are discussed. The theoretical predictions
are experimentally confirmed by the redox reaction of azobenzene in the presence of hydrogen peroxide as an oxidizing agent.
Electronic Publication 相似文献
265.
Summary A method for the determination of chromium(VI) in solid materials with a Cr(VI) content at ppm level in the presence of ca. 10% Cr(III) has been devised. Chromium(VI) is extracted with 0.1M NaOH in a double-water bath (97° C) for 90 min. Differential-pulse polarography in 1M NaOH and spectrophotometry with 1,5-diphenylcarbazide have been tested for use in the final determination of Cr(VI). After extraction in the form of dithiocarbamate into methylisobutylketone or ethylacetate, chromium was determined by flame AAS and DPP in an organic extract. 相似文献
266.
K. Južnič 《Mikrochimica acta》1983,80(5-6):345-348
Summary The sorption of Ce3+ from hydrochloric acid and its chromatography on a column filled with Dowex 50 X8 was studied. The break-through volumes and elution volumes, together with the sorption profile and band broadening were determined at different temperatures and are discussed. The Chromatographic results are interpreted in terms of cerium complex formation.
Über das Verhalten von Cerium(III) in salzsaurer Lösung
Zusammenfassung Die Sorption von Ce3+ aus salzsaurer Lösung in einer mit Dowex 50 X8 gefüllten Säule sowie dessen Chromatographie wurden untersucht. Die Durchbruchs- und Elutionsvolumina wurden bestimmt und diskutiert. Die Ergebnisse wurden im Sinne einer Komplexbildung interpretiert.相似文献
267.
Jandera P Skeifíková V Rehová L Hájek T Baldriánová L Skopová G Kellner V Horna A 《Journal of separation science》2005,28(9-10):1005-1022
Methods were developed for the analysis of natural antioxidants including phenolic compounds and flavonoids in beverages and plant extracts using gradient HPLC with multi-channel electrochemical coulometric detection. Suitability of various reversed-phase columns for this purpose was compared; pH and mobile phase gradients were optimized with respect to the separation selectivity and sensitivity of detection. Because of different target compounds in various sample types, the overlapping resolution maps and the normalized resolution product approaches described earlier were used to select optimum columns and gradients to suit the analysis of the individual sample types. The methods were applied to the analysis of phenolic compounds and flavonoids in beer, wine, tea, and yacon extracts. 32 phenolic compounds were identified and determined, including derivatives of benzoic and cinnamic acids, flavones, and a few related glycosides. Eight-channel CoulArray detection offers high selectivity and sensitivity with limits of detection in the low microg L(-1) range, at least an order of magnitude lower than single-channel coulometric detection using the Coulochem detector. No special sample pretreatment is necessary and, because of the compatibility of the CoulArray detector with gradient elution, phenolic antioxidants of different polarities can be determined in a single run. In addition to the retention times, the ratios of the areas of the pre-dominant and post-dominant peaks to the area of the dominant peak can be used for improved identification of natural antioxidants. 相似文献
268.
Ivanauskas F. Kaunietis I. Laurinavičius V. Razumienė J. Šimkus R. 《Journal of mathematical chemistry》2005,38(3):355-366
The plate-gap model of porous enzyme doped electrode has been proposed and analyzed. It was suggested that reaction diffusion conditions in pores of bulk electrode resemble particular conditions in thin gap between parallel conducting plates. The model is based on the diffusion equations containing a nonlinear term related to the Michaelis–Menten kinetic of the enzymatic reaction inside gap. Steady state current was calculated for the wide range of given parameters and substrate concentrations. All dependences of current on substrate concentration were approximated by hyperbolas in order to obtain “apparent” parameters (maximal currents and apparent Michaelis constants) of modelled biosensors. Simple approximate relationships between given and apparent parameters were derived. The applicability of theoretical plate-gap model was tested for the case of carbon paste electrodes which were doped with PQQ – dependent glucose dehydrogenase. It was found, that soluble glucose dehydrogenase based biosensors exhibit characteristic features of the theoretical plate-gap biosensors. 相似文献
269.
B. Bareika R. Danielius G. Dikchius R. Gadonas A. Piskarskas V. Sirutkaitis R. L. Fork C. V. Shank R. Yen C. Hirlimann W. J. Tomlinson P. Hříbek V. Kubeček M. Vrbová I. S. Ruddock R. Illingworth L. Reekie D. P. Weitekamp K. Duppen D. A. Wiersma 《Applied physics. B, Lasers and optics》1982,29(3):176-179
270.
The paper shows a computer-assisted procedure for the optimization of selectivity of two columns coupled in series by tuning the working temperature (using the isothermal mode) and columns coupling-point pressure at constant inlet and outlet carrier gas pressures. The optimization procedure validation was tested by the separation of 32 hydrocarbons in a column series with the aim to resolve the maximum number of components in the shortest possible analysis time.Dedicated to Professor J. F. K. Huber on the occasion of his 65th birthday 相似文献